Functionalization Of Olefins:Construct C-C And C-O Bonds

This thesis is mainly about olefin functionalization to construct new C-C bond and C-O bond,which is divided into the following three parts.AlC13 catalyzed Oxa-Diels-Alder reaction of aromatic aldehydes with simple dienes:In this work,we have developed an AlCl3 catalyzed Oxa-Diels-Alder reaction between unactivated 1,3-dienes and arylaldehydes.This reaction is characterized by good functional group compatibility,for instance,F,Cl,CN,NO2,OMe and thiophenyl groups are tolerated.This reaction is efficient;one equivalent of dienes is enough to deliver product in good yield for most of the substrates.This regioselective and diastereoselective reaction has expanded the substrate scope to more dienes and aryl aldehydes with a readily available catalyst.Iron Catalyzed Alkyl Heck-Type Reaction of Vinylarenes with Alkyl Diacyl Peroxides:In this work,we have developed the iron catalyzed alkyl Heck-type reaction between olefins and alkyl diacyl peroxides.The reaction conditions are simple,clean,and easy to handle.No reagents other than the substrate,solvent,and iron catalyst are needed,and no hazardous waste is generated.The products are obtained in up to 97%yields in one isomer for most situations using 2.5-5 mol%catalyst.This reaction is compatible with a broad range of functional groups such as the carboxyl,boronic acid,methoxyl,ester,amine,and halide groups.A mechanism involving radicals and carbocation is proposed based on mechanistic experiments.Iron-Catalyzed Decarboxylative Alkyl Etherification of Vinylarenes with Aliphatic Acids as the Alkyl Source:In this work,a variety of alkyl diacyl peroxides and peresters generated from aliphatic acids have been found to enable the first iron-catalyzed alkyl etherification of olefins with general alkyl groups.Primary,secondary and tertiary aliphatic acids are suitable for this reaction,delivering products with yields up to 97%.Primary and secondary alcohols react well,affording products in up to 91%yield.